DE3883854T2 - Process for the production of rigid foams. - Google Patents
Process for the production of rigid foams.Info
- Publication number
- DE3883854T2 DE3883854T2 DE88304805T DE3883854T DE3883854T2 DE 3883854 T2 DE3883854 T2 DE 3883854T2 DE 88304805 T DE88304805 T DE 88304805T DE 3883854 T DE3883854 T DE 3883854T DE 3883854 T2 DE3883854 T2 DE 3883854T2
- Authority
- DE
- Germany
- Prior art keywords
- process according
- polyisocyanate mixture
- mass
- polyisocyanate
- polyisocyanates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000006260 foam Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 43
- 239000005056 polyisocyanate Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 38
- -1 polymethylene Polymers 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 9
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000005829 trimerization reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 238000005187 foaming Methods 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000011495 polyisocyanurate Substances 0.000 description 9
- 229920000582 polyisocyanurate Polymers 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229920002396 Polyurea Polymers 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920003226 polyurethane urea Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- PICMRYFDCLFDAA-UHFFFAOYSA-N CN(C1CCCCC1)C.ClC(F)(Cl)Cl Chemical compound CN(C1CCCCC1)C.ClC(F)(Cl)Cl PICMRYFDCLFDAA-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
Diese Erfindung betrifft Hartschaumstoffe und insbesondere ein Verfahren zur Herstellung von polymeren Hartschaumstoffen, die aus bestimmten Polymethylenpolyphenylpolyisocyanat-Mischungen erhalten werden.This invention relates to rigid foams and, more particularly, to a process for producing rigid polymeric foams obtained from certain polymethylene polyphenyl polyisocyanate mixtures.
Polymethylenpolyphenylpolyisocyanat-Mischungen werden großtechnisch hergestellt, indem Mischungen von Polyaminen, die durch die saure Kondensation von Anilin und Formaldehyd erhalten werden, phosgeniert werden. Die Polyisocyanat-Mischungen, die größte kommerzielle Bedeutung erlangt haben, haben etwa 30 bis etwa 70 Masse% Diphenylmethandiisocyanat zusammen mit verschiedenen Mengen verwandter Methylen-überbrückter Polyphenylentribis -penta- und höherer -polyisocyanate enthalten, wobei die tatsächlichen Zusammensetzungen zum größten Teil von dem anfänglichen Anilin/Formaldehyd-Verhältnis abhängen.Polymethylene polyphenyl polyisocyanate blends are produced on a large scale by phosgenating mixtures of polyamines obtained by the acidic condensation of aniline and formaldehyde. The polyisocyanate blends which have achieved greatest commercial importance have contained from about 30 to about 70% by weight of diphenylmethane diisocyanate together with various amounts of related methylene-bridged polyphenylene tribis-penta- and higher polyisocyanates, the actual compositions depending largely on the initial aniline/formaldehyde ratio.
Solche Mischungen sind in Formulierungen auf Isocyanatbasis vieler Typen und insbesondere bei der Herstellung von Polyurethan- und Polyisocyanurat-Hartschaumstoffen, wie beispielsweise in den GB-Patentschriften 848671, 874430, 1146661, 1184893 und 1223415 beschrieben, verwendet worden.Such mixtures have been used in isocyanate-based formulations of many types and in particular in the manufacture of rigid polyurethane and polyisocyanurate foams, as described, for example, in GB Patent Specifications 848671, 874430, 1146661, 1184893 and 1223415.
GB 1443641 betrifft Polyisocyanurat-Hartschaumstoff-Mischungen, die aus Polymethylenpolyphenylpolyisocyanat erhalten werden. Die Isocyanatkomponente ist dadurch gekennzeichnet, daß sie weniger als 30 Masse% Diisocyanat enthält.GB 1443641 relates to polyisocyanurate rigid foam mixtures obtained from polymethylene polyphenyl polyisocyanate. The isocyanate component is characterized in that it contains less than 30% by weight of diisocyanate.
Es ist nun gefunden worden, daß aus Polymethylenpolyphenylpolyisocyanat-Mischungen, die verminderte Gehalte an Diisocyanaten und Polyisocyanaten mit höherer Molmasse und entsprechend erhöhte Gehalte an Tri- bis Pentaisocyanaten haben, bessere Hartschaumstoffe hergestellt werden können. Insbesondere ist gefunden worden, daß aus den erwähnten Mischungen Polyisocyanurat- Schaumstoffe, die verbesserte Brandschutzeigenschaften, wie sie durch den Sauerstoff-Index gemessen werden, haben, und Polyurethan-Schaumstoffe, die verbesserte Oberflächeneigenschaften, insbesondere eine geringere Bröckligkeit der Oberfläche, haben, hergestellt werden können.It has now been found that better rigid foams can be produced from polymethylene polyphenyl polyisocyanate mixtures which have reduced contents of diisocyanates and polyisocyanates with a higher molecular weight and correspondingly increased contents of tri- to pentaisocyanates. In particular, it has been found that polyisocyanurate foams which have improved fire protection properties, as measured by the oxygen index, and polyurethane foams, which have improved surface properties, in particular less surface brittleness.
Demgemäß wird durch die Erfindung ein Verfahren zur Herstellung von Hartschaumstoffen bereitgestellt, bei dem eine Polymethylenpolyphenylpolyisocyanat-Mischung unter Schaumbildungsbedingungen mit einer polyfunktionellen aktiven Wasserstoff enthaltenden Verbindung zur Reaktion gebracht wird, wobei die Polyisocyanat-Mischung nicht mehr als 20 Masse% Diisocyanate und nicht mehr als 20 Masse% Polyisocyanate, die pro Molekül mehr als 5 Isocyanatgruppen enthalten, enthält.Accordingly, the invention provides a process for producing rigid foams in which a polymethylene polyphenyl polyisocyanate mixture is reacted under foaming conditions with a polyfunctional active hydrogen-containing compound, the polyisocyanate mixture containing not more than 20% by weight of diisocyanates and not more than 20% by weight of polyisocyanates containing more than 5 isocyanate groups per molecule.
Typische Polyisocyanat-Mischungen für die Verwendung bei dem Verfahren der Erfindung enthalten, auf die Masse bezogen:Typical polyisocyanate mixtures for use in the process of the invention contain, by mass:
0 - 20 % Diphenylmethandiisocyanate,0 - 20 % diphenylmethane diisocyanates,
40 - 80 % Dimethylentriphenylentriisocyanate,40 - 80 % dimethylenetriphenylene triisocyanates,
5 - 25 % Polymethylenpolyphenylentetra- und -pentaisocyanate5 - 25 % polymethylenepolyphenylenetetra- and pentaisocyanates
und 0 - 20 % höhere Polymethylenpolyphenylenpolyisocyanate.and 0 - 20 % higher polymethylene polyphenylene polyisocyanates.
Bevorzugte Polyisocyanat-Mischungen für die Verwendung bei dem Verfahren der Erfindung haben einen NCO-Wert, der im Bereich von 32 - 33,3 Masseprozent liegt.Preferred polyisocyanate mixtures for use in the process of the invention have an NCO value that is in the range of 32 - 33.3 mass percent.
Es wird bevorzugt, daß der Diisocyanat-Gehalt der Polyisocyanat-Mischung weniger als 15 Masse% beträgt. Es wird auch bevorzugt, daß der Gehalt an Polyisocyanaten mit 6 oder mehr NCO- Gruppen weniger als 10 Masse% beträgt. Geeignete Mischungen haben vorzugsweise Viskositäten von weniger als 1000 Zentipoise bei 25 ºC.It is preferred that the diisocyanate content of the polyisocyanate mixture is less than 15% by weight. It is also preferred that the content of polyisocyanates with 6 or more NCO groups is less than 10% by weight. Suitable mixtures preferably have viscosities of less than 1000 centipoise at 25°C.
Polyisocyanat-Mischungen, die bei dem Verfahren der Erfindung verwendet werden können, und Verfahren zu ihrer Herstellung sind nach dem Stand der Technik beispielsweise in DE-OS 3245678 und EP 133538 beschrieben worden. Die Mischungen werden im allgemeinen durch Lösungsmittelextraktionsverfahren hergestellt, die mit den ursprünglichen Polymethylenpolyphenylpolyamin-Mischungen vor der Phosgenierung oder mit den entsprechenden Polymethylenpolyphenylpolyisocyanaten durchgeführt werden. Etwaiges überschüssiges Diisocyanat kann dann durch Destillation entfernt werden.Polyisocyanate mixtures which can be used in the process of the invention and processes for their preparation have been described in the prior art, for example in DE-OS 3245678 and EP 133538. The mixtures are generally prepared by solvent extraction processes which are carried out with the original polymethylenepolyphenylpolyamine mixtures before phosgenation or with the corresponding polymethylene polyphenyl polyisocyanates. Any excess diisocyanate can then be removed by distillation.
Im einzelnen ist in DE 3245678 ein Verfahren zur Erzielung einer Polyisocyanat-Mischung durch Phosgenierung einer Polyaminfraktion, die mindestens 94 Masse% Triamine enthält, beschrieben. Die Polyaminfraktion wird bei der fraktionierten Destillation einer Mischung erhalten, die Di- und Polyphenylenpolymethylenpolyamine enthält und aus der sauren Kondensation von Anilin und Formaldehyd resultiert.In detail, DE 3245678 describes a process for obtaining a polyisocyanate mixture by phosgenation of a polyamine fraction containing at least 94% by mass of triamines. The polyamine fraction is obtained by fractional distillation of a mixture containing di- and polyphenylenepolymethylenepolyamines and resulting from the acid condensation of aniline and formaldehyde.
Polyfunktionelle aktiven Wasserstoff enthaltende Verbindungen, die bei dem Verfahren der Erfindung verwendet werden können, schließen Polyole, Polyamine und Wasser ein, die jeweils unter Bildung von Polyurethan- und Polyharnstoff-Produkten mit Polyisocyanaten reagieren. Das Polyisocyanat kann mit den aktiven Wasserstoff enthaltenden Verbindungen in ungefähr stöchiometrischen Mengen zur Reaktion gebracht werden (NCO-Index 100), oder es können alternativ höhere NCO-Indizes, beispielsweise 500 oder 1000 oder noch höher, zusammen mit Trimerisierungskatalysatoren angewandt werden, um Polyisocyanurat-modifizierte Produkte zu bilden.Polyfunctional active hydrogen-containing compounds that can be used in the process of the invention include polyols, polyamines and water, each of which reacts with polyisocyanates to form polyurethane and polyurea products. The polyisocyanate can be reacted with the active hydrogen-containing compounds in approximately stoichiometric amounts (NCO index 100), or alternatively higher NCO indices, e.g. 500 or 1000 or even higher, can be used together with trimerization catalysts to form polyisocyanurate-modified products.
Brauchbare Polyole und Polyamine schließen die herkömmlichen Materialien ein, die bei der Herstellung von Polyurethan-, Polyharnstoff- und Polyisocyanurat-Hartschaumstoffen verwendet werden oder zur Verwendung vorgeschlagen worden sind.Useful polyols and polyamines include the conventional materials used or proposed for use in the manufacture of rigid polyurethane, polyurea and polyisocyanurate foams.
Geeignete Polyole haben im allgemeinen zwei oder mehr Hydroxylgruppen und Molmassen von 62 bis 1500, wobei die Funktionalität und die Molmasse, die entweder für Polyurethan- oder für Polyisocyanurat-Schaumstoffe zweckmäßig sind, in bekannter Weise gewählt werden. Beispiele für solche Polyole schließen Ethylenglykol, Glycerin, Trimethylolpropan, Triethanolamin und ihre Oxyalkylierungsprodukte mit niedrigerer Molmasse ein. Auch Alkanolamine wie z.B. Monoethanolamin könnten verwendet werden. Andere brauchbare Polyole schließen die Oxyalkylierungsprodukte mit niedrigerer Molmasse von Sorbit, Saccharose und aromatischen Polyaminen wie z.B. Toluylendiamin und Polymethylenpolyphenylpolyaminen sowie Bisphenole und Polyether- und Polyesterpolyole ein.Suitable polyols generally have two or more hydroxyl groups and molecular weights of from 62 to 1500, the functionality and molecular weight being selected in a known manner as appropriate for either polyurethane or polyisocyanurate foams. Examples of such polyols include ethylene glycol, glycerin, trimethylolpropane, triethanolamine and their lower molecular weight oxyalkylation products. Alkanolamines such as monoethanolamine could also be used. Other useful polyols include the lower molecular weight oxyalkylation products of sorbitol, sucrose, and aromatic polyamines such as toluenediamine and polymethylenepolyphenylpolyamines, as well as bisphenols and polyether and polyester polyols.
Geeignete Polyamine haben im allgemeinen zwei oder mehr primäre oder sekundäre Aminogruppen und Molmassen von 60 bis 1500.Suitable polyamines generally have two or more primary or secondary amino groups and molecular weights of 60 to 1500.
Mischungen von Polyolen und/oder Polyaminen und/oder Wasser können verwendet werden.Mixtures of polyols and/or polyamines and/or water may be used.
Die Polyisocyanat-Mischung und die polyfunktionelle aktiven Wasserstoff enthaltende Verbindung können unter herkömmlichen Schaumbildungsbedingungen zur Reaktion gebracht werden. Dies umfaßt im allgemeinen die Herstellung einer Reaktionsmischung, die zusätzlich zu dem Polyisocyanat und der aktiven Wasserstoff enthaltenden Verbindung ein Treibmittel enthält.The polyisocyanate mixture and the polyfunctional active hydrogen-containing compound can be reacted under conventional foaming conditions. This generally involves preparing a reaction mixture containing a blowing agent in addition to the polyisocyanate and the active hydrogen-containing compound.
Solche Reaktionsmischungen können auch andere herkömmliche Bestandteile, beispielsweise Katalysatoren, Tenside, Flammenverzögerungsmittel und Trimerisierungskatalysatoren, enthalten.Such reaction mixtures may also contain other conventional ingredients, such as catalysts, surfactants, flame retardants and trimerization catalysts.
Geeignete Treibmittel schließen inerte flüchtige Flüssigkeiten, insbesondere halogenierte Alkane wie z.B. Trichlorfluormethan und Dichlordifluormethan, ein. In einigen Fällen kann Wasser als Treibmittel zusätzlich zu oder anstelle der inerten Flüssigkeit verwendet werden.Suitable propellants include inert volatile liquids, particularly halogenated alkanes such as trichlorofluoromethane and dichlorodifluoromethane. In some cases, water can be used as a propellant in addition to or instead of the inert liquid.
Tenside, die bei der Schaumstoffherstellung brauchbar sind, schließen Siloxan-Oxyalkylen-Copolymere und herkömmliche nichtionogene Tenside ein. Katalysatoren, die bei der Herstellung von Polyurethan- und Polyharnstoff-Schaumstoffen brauchbar sind, schließen die üblichen tertiären Amine und Zinnverbindungen ein, während Trimerisierungskatalysatoren, die für Polyisocyanurat-Schaumstoffe erforderlich sind, Alkalimetall- und Erdalkalimetallhydroxide, -alkoxide und -alkanoate einschließen. Besonders geeignete Katalysatoren für die Herstellung von Polyisocyanurat-Schaumstoffen schließen Mischungen eines Salzes der Formel: Surfactants useful in foam production include siloxane-oxyalkylene copolymers and conventional nonionic surfactants. Catalysts useful in the production of polyurethane and polyurea foams include the usual tertiary amines and tin compounds, while trimerization catalysts required for polyisocyanurate foams include alkali metal and alkaline earth metal hydroxides, alkoxides and alkanoates. Particularly suitable catalysts for the production of Polyisocyanurate foams include mixtures of a salt of the formula:
und eines Salzes der Formel: and a salt of the formula:
worin M ein Alkalimetall oder Tetraalkylammonium bedeutet, Q ein Metall der Gruppe IIA oder Zink bedeutet und R¹, R² und R³, die gleich oder verschieden sein können, Wasserstoff, niederes Alkyl, Cycloalkyl, Phenyl oder Alkylphenyl bedeuten, ein.wherein M is an alkali metal or tetraalkylammonium, Q is a metal of Group IIA or zinc and R¹, R² and R³, which may be the same or different, are hydrogen, lower alkyl, cycloalkyl, phenyl or alkylphenyl.
Solche Katalysatoren werden besonders bevorzugt, wenn der Isocyanat-Index höher als 500 ist.Such catalysts are particularly preferred when the isocyanate index is higher than 500.
Die Schaumstoffe können unter Anwendung irgendeines der herkömmlichen Misch- und Fertigungsverfahren hergestellt werden. So können wie gewünscht Sprühverfahren oder Formpreß- bzw. Spritzgußverfahren oder Laminierverfahren angewandt werden. Die geringere Bröckligkeit der Oberfläche der Polyurethan-Schaumstoffe ist bei Laminierverfahren besonders nützlich, weil die Haftung zwischen dem Schaumstoff und den Deckmaterialien in bedeutendem Maße verbessert wird.The foams can be manufactured using any of the conventional mixing and manufacturing processes. For example, spraying or compression molding or laminating processes can be used as desired. The reduced surface friability of the polyurethane foams is particularly useful in laminating processes because the adhesion between the foam and the covering materials is significantly improved.
Die Erfindung wird durch die folgenden Beispiele, in denen alle Teile auf die Masse bezogen sind, erläutert, jedoch nicht eingeschränkt.The invention is illustrated, but not limited, by the following examples in which all parts are by mass.
Zwei Polyurethan-Schaumstoffe wurden aus den folgenden Formulierungen hergestellt: Oxypropyliertes Glycerin (OH = 540) Siliconfluid DC-193 (DOW Chemical) N,N-Dimethylcyclohexylamin Dibutylzinndilaurat Trichlorfluormethan PolyisocyanatTwo polyurethane foams were prepared from the following formulations: Oxypropylated glycerin (OH = 540) Silicone fluid DC-193 (DOW Chemical) N,N-Dimethylcyclohexylamine Dibutyltin dilaurate Trichlorofluoromethane Polyisocyanate
Polyisocyanat 1 war eine Polymethylenpolyphenylpolyisocyanat- Mischung mit einem NCO-Wert von 33,0, die 16 Masse% Diisocyanat und 6 Masse% Polyisocyanate mit einer Molmasse von mehr als 650 enthielt.Polyisocyanate 1 was a polymethylene polyphenyl polyisocyanate mixture with an NCO value of 33.0, containing 16% by weight of diisocyanate and 6% by weight of polyisocyanates with a molecular weight of more than 650.
Polyisocyanat 2 war eine herkömmliche Polymethylenpolyphenylpolyisocyanat-Mischung mit einem NCO-Wert von 30,6, die 50 Masse% Diisocyanat enthielt.Polyisocyanate 2 was a conventional polymethylene polyphenyl polyisocyanate mixture with an NCO value of 30.6 containing 50 wt% diisocyanate.
Durch Berührungsprüfung wurde gezeigt, daß die Bröckligkeit der Oberfläche des Schaumstoffs 1 geringer war als die des Schaumstoffs 2.By touch testing it was shown that the friability of the surface of foam 1 was less than that of foam 2.
Polyisocyanurat-Schaumstoffe wurden aus den folgenden Formulierungen hergestellt: Polypropylenglykol 425 Siliconfluid DC-193 (DOW Chemical) Kaliumacetat (50%ige Lösung in Ethylenglykol) N,N-Dimethylcyclohexylamin Trichlorfluormethan Polyisocyanat 1Polyisocyanurate foams were prepared from the following formulations: Polypropylene glycol 425 Silicone fluid DC-193 (DOW Chemical) Potassium acetate (50% solution in ethylene glycol) N,N-Dimethylcyclohexylamine Trichlorofluoromethane Polyisocyanate 1
Drei entsprechende Schaumstoffe wurden dann aus denselben Formulierungen hergestellt, außer daß Polyisocyanat 1 durch Polyisocyanat 2 ersetzt wurde (wie in Beispiel 1).Three corresponding foams were then prepared from the same formulations except that polyisocyanate 1 was replaced by polyisocyanate 2 (as in Example 1).
Die so erhaltenen sechs Polyisocyanurat-Schaumstoffe wurden der Sauerstoff-Index-Prüfung (ASTM 2863) unterzogen, wobei die folgenden Ergebnisse erhalten wurden: Polyisocyanat (wie in Beispiel 1)The six polyisocyanurate foams thus obtained were subjected to the oxygen index test (ASTM 2863) and the following results were obtained: Polyisocyanate (as in Example 1)
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB878712364A GB8712364D0 (en) | 1987-05-26 | 1987-05-26 | Rigid foams |
| US07/414,569 US5356943A (en) | 1987-05-26 | 1989-09-29 | Rigid foams |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE3883854D1 DE3883854D1 (en) | 1993-10-14 |
| DE3883854T2 true DE3883854T2 (en) | 1994-01-20 |
Family
ID=26292285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE88304805T Expired - Fee Related DE3883854T2 (en) | 1987-05-26 | 1988-05-26 | Process for the production of rigid foams. |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5356943A (en) |
| EP (1) | EP0294110B1 (en) |
| JP (1) | JP2675816B2 (en) |
| AU (1) | AU1667988A (en) |
| DE (1) | DE3883854T2 (en) |
| ES (1) | ES2058279T3 (en) |
| ZA (1) | ZA883499B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02196816A (en) * | 1989-01-26 | 1990-08-03 | M D Kasei Kk | Production of integral skin foam |
| DE4001249A1 (en) * | 1990-01-18 | 1991-07-25 | Bayer Ag | Cold formable open cell rigid polyurethane foam prodn. - from specified poly:ol component and crude MDI, used for car canopy |
| GB9021051D0 (en) * | 1990-09-27 | 1990-11-07 | Ici Plc | Catalyst composition |
| US5880167A (en) * | 1994-08-22 | 1999-03-09 | Henkel Kommanditgesellschaft Auf Aktien | Polyurethane compositions with a low content of monomeric diisocyanates |
| US5817860A (en) * | 1998-03-20 | 1998-10-06 | Essex Specialty Products, Inc. | Polyurethane prepolymer compositions, foams made therefrom and methods of making each thereof |
| US6619009B2 (en) | 2001-04-30 | 2003-09-16 | Orbseal Llc | Reinforcement for expandable compositions and methods for using the reinforcement |
| JP2008501060A (en) * | 2004-05-28 | 2008-01-17 | アルベマール・コーポレーシヨン | Flame retarding polyurethane and additives therefor |
| CN101421326B (en) * | 2006-04-12 | 2011-10-26 | 巴斯夫欧洲公司 | Process for preparing polyurethanes |
| US20100076101A1 (en) * | 2006-11-17 | 2010-03-25 | Basf Se | Polyphenylenepolymethylene polyisocyanate and its use for producing polyurethane foams |
| WO2008084054A1 (en) * | 2007-01-12 | 2008-07-17 | Basf Se | Polyurethane rigid foams |
| WO2011127028A1 (en) | 2010-04-09 | 2011-10-13 | Albemarle Corporation | Liquid flame retardant formulation useful for flame lamination applications |
| US20140186611A1 (en) * | 2011-06-29 | 2014-07-03 | Dow Global Technologies Llc | Polyol formulations for improved green strength of polyisocyanurate rigid foams |
| CN109476814B (en) * | 2016-07-21 | 2022-05-10 | 科思创德国股份有限公司 | High temperature stable polyisocyanurate foams |
| US11970570B2 (en) | 2017-09-28 | 2024-04-30 | Albemarle Corporation | Brominated flame retardant and its application in polyurethane foams |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3936483A (en) * | 1964-04-09 | 1976-02-03 | Mobay Chemical Corporation | Organic polyisocyanates |
| US4405725A (en) * | 1967-03-24 | 1983-09-20 | Mobay Chemical Corporation | Foamed polyisocyanurates |
| DD100273A1 (en) * | 1972-01-04 | 1973-09-12 | ||
| JPS5312898B2 (en) * | 1972-08-11 | 1978-05-06 | ||
| GB1433645A (en) * | 1973-01-11 | 1976-04-28 | Celotex Corp | Polyisocyanurate composition related products and processes |
| US4200699A (en) * | 1978-10-12 | 1980-04-29 | M&T Chemicals Inc. | Catalyst composition for rigid polyurethane foams |
| GB2041953A (en) * | 1979-02-08 | 1980-09-17 | Ici Ltd | Rigid polyisocyanurate foams |
| US4256847A (en) * | 1979-10-17 | 1981-03-17 | Mooney Chemicals, Inc. | Rigid polyurethane foam process using lithium/zinc catalyst |
| US4362678A (en) * | 1980-01-18 | 1982-12-07 | The Celotex Corporation | Method of making polyisocyanurate foam laminate |
| US4711912A (en) * | 1982-04-29 | 1987-12-08 | The Celotex Corporation | Polyisocyanurate foams from digestion products of polyalkylene terephthalate polymers and polyols |
| JPS5993038A (en) * | 1982-11-16 | 1984-05-29 | Mitsubishi Chem Ind Ltd | Polyisocyanate composition |
| DE3245678A1 (en) * | 1982-12-10 | 1984-06-14 | Basf Ag, 6700 Ludwigshafen | Polyisocyanate mixtures of isomers and homologues of the diphenylmethane series and their use as adhesive additive |
| US4555418A (en) * | 1983-10-12 | 1985-11-26 | The Celotex Corporation | Alkoxylated aromatic amine-aromatic polyester polyol blend and polyisocyanurate foam therefrom |
| US4623673A (en) * | 1985-10-24 | 1986-11-18 | The Dow Chemical Company | Urethane-modified polyisocyanurate rigid foam |
-
1988
- 1988-05-17 ZA ZA883499A patent/ZA883499B/xx unknown
- 1988-05-26 ES ES88304805T patent/ES2058279T3/en not_active Expired - Lifetime
- 1988-05-26 DE DE88304805T patent/DE3883854T2/en not_active Expired - Fee Related
- 1988-05-26 AU AU16679/88A patent/AU1667988A/en not_active Abandoned
- 1988-05-26 JP JP63129420A patent/JP2675816B2/en not_active Expired - Lifetime
- 1988-05-26 EP EP88304805A patent/EP0294110B1/en not_active Expired - Lifetime
-
1989
- 1989-09-29 US US07/414,569 patent/US5356943A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0294110B1 (en) | 1993-09-08 |
| ES2058279T3 (en) | 1994-11-01 |
| ZA883499B (en) | 1988-11-28 |
| US5356943A (en) | 1994-10-18 |
| JPS63309512A (en) | 1988-12-16 |
| JP2675816B2 (en) | 1997-11-12 |
| AU1667988A (en) | 1988-12-01 |
| EP0294110A1 (en) | 1988-12-07 |
| DE3883854D1 (en) | 1993-10-14 |
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| 8365 | Fully valid after opposition proceedings | ||
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Owner name: HUNTSMAN ICI CHEMICALS LLC, SALT LAKE CITY, UTAH, |
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| 8339 | Ceased/non-payment of the annual fee |